(3aR,7aR)-Octahydro-1,3-dibenzyl-1,3,2-benzodiazaphosphole 2-oxide | 138442-64-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: (3aR,7aR)-Octahydro-1,3-dibenzyl-1,3,2-benzodiazaphosphole 2-oxide
• 英文别名: (3aR,7aR)-2,3,3a,4,5,6,7,7a-Octahydro-1,3-dibenzyl-1H-1,2,3-benzodiazaphosphole-2-oxide；(3aR,7aR)-1,3-dibenzyl-3a,4,5,6,7,7a-hexahydrobenzo[d][1,3,2]diazaphosphole 2-oxide
• CAS: 138442-64-5
• 化学式: C₂₀H₂₅N₂OP
• 分子量: 340.405
• InChiKey: PTIDAWYWVFLUQR-WOJBJXKFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  23.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3aR,7aR)-Octahydro-1,3-dibenzyl-1,3,2-benzodiazaphosphole 2-oxide 在 四氯化锡 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 23.0h， 以30%的产率得到2-chloro-2,3,3a,4,5,6,7,7a-octahydro-1,3-bis(phenylmethyl)-1H-1,3,2-benzodiazaphosphole-2-oxide
  参考文献：
  名称：

  Koeller, Kevin J.; Rath, Nigam P.; Spilling, Christopher D., Phosphorus, Sulfur and Silicon and the Related Elements, 1995, vol. 103, # 1-4, p. 171 - 182

  摘要：

  DOI：
• 作为产物：
  描述：

  (1R,2R)-1,2-diaminocyclohexane 在 水 、 三乙胺 、 三氯化磷 作用下， 以 甲苯 为溶剂， 生成 (3aR,7aR)-Octahydro-1,3-dibenzyl-1,3,2-benzodiazaphosphole 2-oxide
  参考文献：
  名称：

  具有手性二氮杂膦基团的新型磺鎓叶立德作为不对称环丙烷化试剂的合成

  摘要：

  由手性 N,N'-取代（苄基、异丙基、新戊基）膦酰胺衍生的锍叶立德是通过将适当的手性亚磷酸二酰胺与氢化钾和氯甲基甲基硫醚反应制备的，然后在 AgBF4 存在下与甲基碘反应得到相应的锍盐高产量。其中之一通过 X 射线晶体学进行了分析。用不同碱（二异丙基胺锂、锂、碳酸钾）处理后的盐被原位转化为叶立德，叶立德与活化的烯烃反应生成膦酰基环丙烷，作为两种非对映异构体的混合物，具有中等至高的非对映选择性。

  DOI：

  10.1002/hc.21183

文献信息

• The preparation and reactions of chiral phosphorous acid diamides
  作者：Kevin J. Koeller、Christopher D. Spilling

  DOI：10.1016/0040-4039(91)80151-u

  日期：1991.10

  Chiral phosphorous acid diamides were prepared by condensation of N,N′-disubstituted C2 diamines with PCl3 followed by an equivalent of water. Deprotonation of these acids with n-butyl lithium or LDA gave the lithium salt which reacted smoothly with alkyl halides to give the substituted phosphonamides in good yield.

  通过将N，N'-二取代的C 2二胺与PCl 3缩合，然后再加入等价的水来制备手性亚磷酸二酰胺。这些酸用正丁基锂或LDA脱质子化得到的锂盐与烷基卤化物平稳反应，以高收率得到取代的膦酰胺。
• Synthetic and structural chemistry of enantiomerically pure 1-phenyl-2-carboxyethylphosphonic acid and its derivativesElectronic supplementary information (ESI) available: Tables S1–6. See http://www.rsc.org/suppdata/nj/b1/b111244a/
  作者：Stuart Gardner、Majid Motevalli、Kirtida Shastri、Alice C. Sullivan、Peter B. Wyatt

  DOI：10.1039/b111244a

  日期：2002.4.2

  (S)-(+)-1-Phenyl-2-carboxyethylphosphonic acid, (S)-1, has been prepared via diastereoselective alkylation of (3aR,7aR)-octahydro-1,2,3-tribenzyl-1,3,2-benzodiazaphosphole 2-oxide (3) using tert-butyl bromoacetate; the X-ray crystal structure of the intermediate alkylation product is described. The X-ray structure of a single crystal of (R)-1, obtained by crystallisation of rac-1 is reported. The structure

  （S）-（+）-1-苯基-2-羧乙基膦酸（S）-1是通过（3a R，7a R）-八氢-1,2,3-三苄基-1，的非对映选择性烷基化制备的，使用溴乙酸叔丁酯的3,2-苯并二氮杂磷2-氧化物（3）；描述了中间烷基化产物的X射线晶体结构。报道了通过rac - 1的结晶获得的（R）-1单晶的X射线结构。（R）-1的结构显示了涉及P（O）patternHO–C，P–OH⋯（O）C和P（O）⋯HO–P相互作用的分子间氢键的三维模式，但成对的羧基之间没有任何关联。据报道尝试用各种对映体纯的碱拆分rac - 1。报告了水合复盐（R）-1-苯基乙基铵rac -1-苯基-2-羧乙基膦酸酯水合物的X射线结构。该重盐意外地从rac - 1和rac -1-苯基乙胺的产物的水溶液中结晶。
• The synthesis, structure and properties of diazaphospholes: Reagents and ligands for asymmetric synthesis
  作者：Antonette De la Cruz、Kevin J Koeller、Nigam P Rath、Christopher D Spilling、Isabel C.F Vasconcelos

  DOI：10.1016/s0040-4020(98)00502-x

  日期：1998.8

  Reaction of C-2 diamines with PCl3 and Et3N in toluene, followed by water or hydrogen sulfide, gave a series of cyclic phosphorous acid diamides (diazaphosphole oxides) and thiophosphorous acid diamides (diazaphosphole sulfides), respectively. Similarly, reaction of diamines with phenyl dichlorophosphine gave phenyl diazaphospholes. The synthesis, properties, and structure of these diazaphospholes are reported. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Reactions of Chiral Phosphorous Acid Diamides: The Asymmetric Synthesis of Chiral .alpha.-Hydroxy Phosphonamides, Phosphonates, and Phosphonic Acids
  作者：Vincent J. Blazis、Kevin J. Koeller、Christopher D. Spilling

  DOI：10.1021/jo00109a025

  日期：1995.2

  Addition of aldehydes to the anions of chiral phosphorous acid diamides in THF solution gave a-hydroxy phosphonamides in good yield. The diastereoselectivity was strongly dependent upon the diamide used and ranged from poor to good. The phosphorous acid diamides 2a and 2b (R(1) = -(CH2)4-,R(2) = CH(2)Ph and CH(2)CMe(3), respectively) gave the best selectivity, and their reactions with a range of aldehydes were studied. Diamide 2b consistently gave good selectivities, whereas diamide 2a was only moderately selective. Aromatic, aliphatic, and unsaturated aldehydes are tolerated under the reaction conditions. The phosphonamides were hydrolyzed with aqueous HCl in dioxane to give a-hydroxy phosphonic acids. While direct methanolysis of the phosphonamides was unsuccessful, methylation of the phosphonic acids with diazomethane gave alpha-hydroxy dimethylphosphonates.
• Blazis, Vincent; Cruz, Antonette De La; Koeller, Kevin, Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 75, # 1-4, p. 159 - 162
  作者：Blazis, Vincent、Cruz, Antonette De La、Koeller, Kevin、Spilling, Christopher D.

  DOI：——

  日期：——